JPH0267366A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in processability, chemical resistance and heat resistance by blending a resin formed by copolymerizing a styrene monomer or a (meth)acrylate monomer with a monomer having a specified functional group with a liquid crystal polymer. CONSTITUTION:This thermoplastic resin composition is prepaed by blending 10-99wt.% copolymer of a monomer mixture essentially consisting of an aromatic vinyl and/or an alkyl (meth)acrylate with 0.1-30wt.%, especially, 0.3-10wt.% monomer having a functional group selected from among carboxyl, acid anhydride, epoxy, hydroxyl and amino groups with 90-1wt.%, especially, 49-2% liquid crystal polymer (desirably, one which can show optical anisotropy when melted and is melt-processable at 200-350 deg.C), for example, a copolyester comprising 40-70mol% p-hydroxybenzoate, 30-15mol% aromatic dicarboxylic acid and 30-15mol% aromatic diol.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a thermoplastic resin composition having excellent processability, chemical resistance and heat resistance. More specifically, the present invention relates to a thermoplastic resin composition that has significantly improved processability, chemical resistance, and heat resistance by blending a styrene resin with a liquid crystal polymer.

b. Prior art acrylonitrile-polybutadiene-styrene (ABS
) Resin, acrylonitrile - ethylene propylene rubber -
Styrenic resins, including styrene (AES) resin, acrylonitrile-styrene (AS) resin, and methyl methacrylate-styrene (MS) resin, are widely used in industry due to their excellent mechanical properties and excellent moldability. It is used for a wide range of purposes.

These resins lack heat resistance and mechanical strength depending on their use, so inorganic fillers such as glass fiber are added to improve these properties. Furthermore, in order to improve chemical resistance, blending of a crystalline resin with the above-mentioned inorganic filler has recently been carried out.

However, adding inorganic fillers such as glass fibers to improve the rigidity of styrenic resins improves the elastic modulus, heat resistance, and chemical resistance, but may cause wear of the molding machine during molding or increase the melt viscosity. Therefore, a problem arises in that workability is reduced. Furthermore, the appearance of the resulting molded product is often poor.

In order to solve these drawbacks, crystalline resins such as polyamide (Japanese Unexamined Patent Publication No. 58-93745), PPE resins (
Attempts have been made to add heat-resistant resins such as JP-A-59-193951) or polysulfone, styrene-maleic anhydride resin, but adding crystalline resins results in insufficient heat resistance, and adding heat-resistant resins results in insufficient heat resistance. It is often strong and brittle.

C9 Problems to be Solved by the Invention The present inventors have made intensive studies to obtain a styrenic resin composition with excellent processability, chemical resistance, and heat resistance. It has been discovered that a thermoplastic resin excellent in the above points can be obtained by blending in a specific ratio, and the present invention has been achieved.

60 Means for Solving the Problems, that is, the thermoplastic resin composition of the present invention has (a) at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group. Resins 10 to 99 whose essential components are aromatic vinyl and/or (meth)acrylic acid alkyl esters, in which at least one copolymerizable monomer is copolymerized in an amount of 0.1 to 30% by weight. (b) 90-1% by weight of liquid crystal polymer.

The resin of component (a) of the present invention includes (1) a copolymer obtained by copolymerizing an aromatic vinyl and/or (meth)acrylic acid alkyl ester with a copolymerizable monomer having a functional group; Combined resin; (2)
A copolymer resin obtained by further adding a copolymerizable monomer to (1) and copolymerizing it; (3) In the presence of a rubbery polymer, the above (1) or (
A graft copolymer resin obtained by polymerizing the monomer of (2); (4) the above (1) or (2) in the presence of a rubbery polymer modified with a monomer having a functional group; A graft copolymer resin obtained by polymerizing the monomers; or (5)
Do not copolymerize monomers with functional groups with the above (1), (2), (3), (4), etc. (1), (2), (3)
, (4), etc.

When the resin of component (a) is mainly composed of aromatic vinyl, it has excellent processability, while when it is composed mainly of (meth)acrylic acid alkyl ester, it has poor weather resistance and chemical resistance. Excellent.

Examples of the aromatic vinyls mentioned above include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, motsupromustyrene, dibromustyrene, p-tert-butylstyrene, ethylstyrene, and vinylnaphthalene. , these are 1
Used in one species or in combination of two or more. A preferred aromatic vinyl is styrene.

As the above (meth)acrylic acid alkyl ester, (
Methyl acrylate, ethyl (meth)acrylate,
Propyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. may be used, and one or more of these may be used. Can be done. A preferred alkyl (meth)acrylate is methyl (meth)acrylate.

Examples of copolymerizable monomers having the above functional groups include carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, and amino groups that are copolymerizable with aromatic vinyl compounds and/or (meth)acrylic acid alkyl esters. At least one compound having at least one functional group selected from the following is used. This can improve the compatibility between component (a) and the liquid crystal polymer.

Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred.

These may be used alone or in combination of two or more.

Examples of unsaturated compounds containing acid anhydride groups include maleic anhydride, itaconic anhydride, and chloromaleic anhydride.
A particularly preferred compound is maleic anhydride.

Examples of the epoxy group-containing unsaturated compound include compounds each having an unsaturated group and an epoxy group in the molecule that can be copolymerized with an olefin and an ethylenically unsaturated compound.

Preferred epoxy group-containing unsaturated compounds include the following -
Examples include the compound represented by ``Funajin'' and the compound represented by ``Funajin'' below.

Preferred specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, and particularly preferred epoxy group-containing unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc. is mentioned. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing unsaturated compound include compounds that have at least one unsaturated bond and also contain a hydroxyl group. Typical examples thereof include alcohols having double or triple bonds, esters of -valent or divalent unsaturated carboxylic acids, and unsubstituted dihydric alcohols. Among the hydroxyl group-containing unsaturated compounds, suitable examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and 2,3,4.5-tetrahydroxy. Acrylic acid, ester, methacrylic acid ester such as pentyl acrylate, 3-hydroxy-1
-propene, 4-hydroxy-1-butene, trans
-1,4-dihydroxy-2-butene, etc.
These may be used alone or in combination of two or more.

Particularly preferred hydroxyl group-containing unsaturated compounds are 2
-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate and 3-hydroxylpropyl methacrylate.

Examples of unsaturated compounds containing an amino group include vinyl monomers having at least one of the following amino groups or substituted amino groups, and specific examples include acrylamide, methacrylamide, and N-methylacrylamide. acrylamide or methacrylamide derivatives, such as
Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminoethyl acrylate, aminopropyl methacrylate, dimethylaminoethyl methacrylate, and phenylaminoethyl methacrylate; vinyl amines such as N-vinyldiethylamine and N-acetylvinylamine; derivatives, allylamine, methacrylamine, N
- Allylamine derivatives such as methylallylamine and aminostyrenes such as P-aminostyrene. These amino group- or substituted amino group-containing unsaturated compounds may be used alone or in combination of two or more.

Particularly preferred amino group-containing unsaturated compounds are (meth)acrylamide derivatives such as acrylamide and methacrylamide.

The amount of the various functional group-containing monomers used in the resin (a) ranges from 0.1 to 30% by weight, preferably from 0.2 to 30% by weight.
The coulometric content is 20% by weight, more preferably 0.3 to 10% by weight. If it is less than 0.1% by weight, the compatibility between the liquid crystal polymer (b) component and the styrene resin which is the component (a) to be blended will be poor; if it exceeds 30% by weight, the heat resistance and fluidity will be poor. This is not desirable as it may cause a decrease in

Examples of the copolymerizable monomers in (2) above include vinyl cyanide compounds such as acrylonitrile and methacrylate, and acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and phenyl acrylate. methacrylic acid alkyl esters IN such as methyl methacrylate, octyl methacrylate, hexyl methacrylate, and dodecyl methacrylate, maleimide compounds such as N-phenylmaleimide, N-octylmaleimide, and N-cyclohexylmaleimide, and monomers that can be copolymerized with these. One type or two or more types can be used.

The rubbery polymer in the graft copolymer resin of (3) above is preferably 5 to 80%, preferably 10 to 80%.
Thermoplastic styrene-butadiene copolymers, styrene-ethylene copolymers, styrene-propylene copolymers, and other block copolymers containing 50% by weight and a content of polybutadiene, polyisoprene, and styrene of 50% by weight or less There are olefin rubbers such as rubber, acrylic rubber, nitrile rubber, chlorinated polyethylene, EPDM, and EPM, and these may be used alone or in combination of two or more.

Specific examples of modifiable styrenic resins useful for the purposes of the present invention include polystyrene, styrene-acrylonitrile copolymers (^S resins), MS resins, and the like.

In addition, examples of graft polymers that can be modified using rubber-like polymers as substrates include ABS resin, methyl methacrylate-
Polybutadiene-styrene (MBS) resin, ABS resin, acrylonitrile-chlorinated polyethylene-styrene (
AC5) Resin, etc. can be mentioned.

The resin which is component (a) of the present invention can be produced by a known polymerization method, such as an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, a solution polymerization method,
Polymerization can be carried out by a bulk-suspension polymerization method or a bulk-solution polymerization method.

The liquid crystal polymer which is the component Φ) of the present invention is a so-called thermotropic liquid crystal polymer that exhibits optical anisotropy when melted, and has a temperature of 100 to 400°C, preferably 150 to 370°C, and more preferably 150 to 370°C. 200-3
Refers to products that can be melt-processed at 50°C and the resulting molded products exhibit excellent mechanical properties. Specifically, fully aromatic polyester, aromatic-aliphatic polyester, fully aromatic polyester amide, aromatic-aliphatic polyester amide, aromatic polyazomethine, aromatic polyester carbonate, and rigid portions exhibiting liquid crystallinity in their side chains. Examples include side chain type liquid crystal polymers having (mesogen groups) and mixtures thereof.

The above-mentioned fully aromatic polyester includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-dicarboxynaphthalene, hydroquinone, methylhydroquinone, phenylhydroquinone, chlorohydroquinone,
Diols and p
-hydroxybenzoic acid, m-hydroxybenzoic acid, 2.
It consists of a copolymer of aromatic hydroxycarboxylic acids such as 6-dimethylhydroxybenzoic acid.

In addition to the monomers used in the aromatic polyester, the aromatic-aliphatic polyester contains trans -1,
4-dicarboxycyclohexane, cis -1°4-
Dicarboxycyclohexane, alicyclic dicarboxylic acids consisting of alkyl and aryl substituted products of these, ethylene glycol, 1,4-butanediol, trans-1,4
- Consists of a compound copolymerized with an appropriate amount of alicyclic or aliphatic diol such as dihydroxycyclohexane.

Among the above fully aromatic polyesters and aromatic-aliphatic polyesters, preferred as component (b) of the present invention are (1) 40 to 70 mol% of p-hydroxybenzoic acid and 30 to 15% of the above aromatic dicarboxylic acid. Copolyester consisting of mol% and 30 to 15 mol% of aromatic diol: (2
) A copolyester consisting of terephthalic acid and/or isophthalic acid and chlorohydroquinone, phenylhydroquinone, tert-butylhydroquinone and/or hydroquinone; (3) 20 to 80 mol% of p-hydroxybenzoic acid and 2-hydroxynaphthalene-6
-Copolyester consisting of 80 to 20 mol% of carboxylic acid; (4) Copolyester formed by copolymerizing 50 to 80 mol% of p-hydroxybenzoic acid and 50 to 20 mol% of polyethylene terephthalate;

Further, the fully aromatic polyester amide and the aromatic-aliphatic polyester amide include the polyester,
It is a copolymer of aromatic amines such as p-aminobenzoic acid, p-phenylenediamine, m-phenylenediamine, and aliphatic diamines such as hexamethylenediamine.

The above-mentioned aromatic polyazomethine is represented by the symbol ``?'' below. It is a compound containing a zometine moiety in its aromatic main chain.

A compound contained in the main chain.

The above-mentioned side chain type liquid crystal polymer is a liquid crystal polymer having a repeating unit of the following structural formula in which a mesogenic group is connected as a side chain to an ethylene-based main chain, a siloxane-based main chain, or the like.

The above-mentioned aromatic polyester carbonate has a carbonate ester moiety represented by the following symbol R, where R is a hydrogen atom or a methyl group, and n is an integer from 0 to I2. However, when n=0, -0-(CH2±70- is -O-. Also, X has a structure selected from the following -Sailor).

These liquid crystal polymers generally have a higher melting temperature than the styrene resin, which is component (a), so when a liquid crystal polymer with a very high melting temperature and a styrene resin are melt-processed,
Since thermal deterioration of styrenic resin occurs during processing, in practice, the processing temperature of styrenic resin (
In general, temperatures close to 300°C or lower are preferably used.

Preferred liquid crystal polymers include fully aromatic polyesters, aromatic-aliphatic polyesters, fully aromatic polyesteramides, aromatic-aliphatic polyesteramides, aromatic polyazomethines, aromatic polyester carbonates, and side chains having a melting temperature of 300°C or less. type liquid crystal polymer is used.

Specifically, fully aromatic polyesters and aromatic aliphatic polyesters include: (1) fully aromatic polyesters consisting of p-hydroxybenzoic acid, aromatic dicarboxylic acids, and aromatic diols with a melting point of 300°C or lower; .

(2) Among copolyesters consisting of terephthalic acid and/or isophthalic acid and chlorohydroquinone, phenylhydroquinone, tert-butylhydroquinone and/or hydroquinone, those having a melting point of 300″C or less.

(3) Among copolyesters consisting of P-hydroxybenzoic acid and 2-hydroxynaphthalene-6-carboxylic acid, those having a melting point of 300°C or less.

(4) Among copolyesters formed by copolymerizing p-hydroxybenzoic acid and polyethylene terephthalate, those having a melting point of 300'C or less.

etc., by copolymerizing the polyesters (1) to (4) above with aromatic diamines such as p-aminobenzoic acid, p-phenylenediamine, and m-phenylenediamine, and aliphatic diamines such as hexamethylenediamine. , fully aromatic polyesteramides and aromatic-aliphatic polyetheramides can be obtained, but these can also be suitably used if their melting points are below 300°C.

In addition, aromatic polyazomethine, aromatic polyester carbonate, and side chain type liquid crystal polymer having a melting point of 300° C. or lower are preferably used.

More preferred liquid crystal polymers include fully aromatic polyesters, aromatic-aliphatic polyesters, and fully aromatic polyester amides, since they have a melting temperature close to that of styrene resins and improve chemical resistance and processability, which are the objectives of the present invention. , aromatic-aliphatic polyesteramides are used.

These (b) components are blended in the thermoplastic resin composition of the present invention in an amount of 90 to 1% by weight, preferably 60 to 1% by weight.
It is blended in a range of 2% by weight. Furthermore, 49-2% by weight
When blended within this range, the effects of the present invention which are much more excellent can be obtained. If the amount is less than 1% by weight, no significant effect on improving processability and chemical resistance will be observed.

On the other hand, if it exceeds 90% by weight, the properties approach the original properties of the liquid crystal polymer, resulting in strength anisotropy and the resulting molded product having poor appearance.

Various extruders, Banbury mixers, kneaders, rolls, etc. are used for kneading to obtain the thermoplastic resin of the present invention. A preferred kneading method is a method using an extruder.

The kneading temperature needs to be higher than the melting points of the styrenic resin (a) component and the liquid crystal polymer C#3) component to be mixed, and is preferably about 200 to 350°C.

When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos,
Fillers such as wallasnite, calcium carbonate, talc, barium sulfate, etc. may be used alone or in combination. Alternatively, a thermoplastic resin composition can be obtained by mixing fibers of the liquid crystal polymer (component (b)) at a temperature below its melting point.

Among these fillers, glass fibers, carbon fibers, and liquid crystal polymer fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.

These fillers can be mixed in an amount of 1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin composition of the present invention, depending on the purpose.

Additionally, known additives such as flame retardants, antioxidants, plasticizers, colorants, and lubricants may be added.

Furthermore, depending on the purpose, other rubbery polymers and thermoplastic elastomers may be used in combination to further improve impact resistance.

Rubbery polymers that can be used in combination include, in addition to those mentioned in the production of the graft polymer, fluororubber, silicone rubber, chloroprene rubber, butyl rubber, halogenated butyl rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, and ethylene acetic acid. Examples include liquid rubbers such as vinyl copolymers, polysulfide rubbers, epichlorohydrin rubbers, urethane rubbers, butadiene rubbers, and nitrile rubbers modified with carboxyl groups or amino groups, and these may be used singly or in combination of two or more depending on the purpose. Ru.

Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, MMA resin, PET,
PBT, PPE, polyamide, polycarbonate, polyacetal, polyacrylate, polysulfone, polyethersulfone, PPS, polyetheretherketone, polyimide, fluororesin such as polyvinylidene fluoride, etc. can be blended as appropriate.

The thermoplastic resin composition of the present invention can be used as various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like. Particularly in injection molding, in order to orient the liquid crystal polymer (component (b)),
It is preferable to mold at a sufficient injection speed.

The various molded products obtained by the above molding method can be used for automobile exterior and interior parts, various electrical and electronic related parts, housings, etc. by utilizing their excellent properties.

e. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are merely illustrative and do not limit the content of the present invention.

In addition, in the following examples, parts and % indicate parts by weight and % by weight, respectively.

(Production Example I) Styrenic substrate (modified AS resin) M-1-
Preparation of M-5: In a 7 liter glass flask equipped with a stirrer,
After adding the chemical solution shown in 1 and displacing the air inside with nitrogen, the inside was heated to 50°C while controlling the jacket to 70"C, and potassium persulfate dissolved in 4 parts of water was added.
．． 3 parts and 0.1 part of sodium sulfite dissolved in 1 part of water were added and reacted for 3 hours.

Calcium chloride was added to the obtained styrenic matrix polymer latex at a ratio of 2 parts to 100 parts of polymer, and 9
It solidified at 0''C. This was separated, washed with water, dehydrated, and dried to obtain styrenic substrates M-1 to M5 shown in Table 1.

(Production Example 2) Graft copolymer resins G-1 and G-2
Preparation: In a 7 liter glass flask equipped with a stirrer,
After adding the batch-prepared chemical solution shown in 2 and purging the inside with nitrogen, the inside was heated to 40°C while controlling the jacket at 70°C, and 0.2 parts of sodium pyrophosphate dissolved in 10 parts of water was added. 3 parts of dextrose, 0.35 parts of dextrose, and 0.01 part of ferrous sulfate, and 0.1 part of cumene hydroperoxide were added and reacted.

One hour after starting the reaction, the incremental mixture shown in Table 2 was added continuously over a period of three hours, and the reaction was continued for an additional hour.

2,6-di-tert-butyl para-cresol 1 was added to the obtained graft copolymer latex as an anti-aging agent.
．． After adding 0 parts, sulfuric acid was added at a ratio of 2 parts to 100 parts of polymer and coagulated at 90°C. Separate this,
After washing with water, dehydration, and drying, graft copolymers G-1 and G-2 shown in Table 2 were obtained.

G1, G Examples 1 to 7 and Comparative Examples 1 to 5: Styrenic substrates M-1 to M5 obtained in Production Example 1, G-1 obtained in Production Example 2, G-2 and Japanese synthetic rubber ■
5240 to styrene-acyclonitrile copolymer resin
(24.5% by weight of bound acrylonitrile, methyl ethyl ketone, η=0.60 at 30"C), and EPE-240 (polyethylene terephthalate)/p-hydroxybenzoic acid copolymer manufactured by Mitsubishi Kasei ■ was used as the liquid crystal polymer. thermotropic liquid crystalline polyester, melt processing temperature range 240-320°C), or Vectra A-950 manufactured by Polyplastics (p-hydroxybenzoic acid/,
Using a thermotropic liquid crystalline aromatic polyester containing 6-hydroxy-2-naphthoic acid as the main component,
The mixture was mixed using a Henschel mixer according to the proportions and conditions shown in Section 3, and granulated using a 30 mm twin-screw vented extruder.

The obtained pellet-shaped thermoplastic resin composition was sufficiently dried in a vacuum dryer, and then molded in an injection molding machine according to the conditions shown in Table 3 to prepare test pieces. Chemical resistance and heat resistance were evaluated, and processability was further evaluated using pellets after drying.

Chemical resistance: A constant strain with a strain rate of 0.5% was applied to a constant strain solvent crack test piece (l/8″ x 115″ x 5), and brake oil (hereinafter referred to as BO) was applied to the deflected part. The time taken to break when the film was left at 23°C was measured. Further, similar measurements were conducted using dioctyl phthalate (hereinafter referred to as DOP) under the condition of a strain rate of 1.0%. The longer the time, the better the chemical resistance.

Heat resistance: 857M according to D648, thickness 1/2",
The heat distortion temperature was measured at a load of 18.6 kg/c1il.

Workability: 260°C1 according to JIS K7210
Melt flow rate (MFR) was measured at a load of 10 kg.

As is clear from the comparison of Examples 1 to 7 and Comparative Example 1 shown in Table 3, the thermoplastic resin composition of the present invention is a resin with excellent chemical resistance and processability.

Since the composition of Comparative Example 2 does not contain a functional group-containing monomer component, it has significantly inferior chemical resistance and improved processability (fluidity) compared to the compositions of Examples 2 and 3. It is also not very effective.

The composition of Comparative Example 3 also does not contain a functional group-containing monomer component, has significantly inferior chemical resistance compared to the composition of Example 4, and has no effect on improving processability (fluidity). is small.

The composition of Comparative Example 4 is an example of a composition containing a styrene substrate containing 35% by weight of methacrylic acid as a functional group-containing monomer component, but the processability is significantly reduced.

Although the composition of Comparative Example 5 is an example in which glass fiber is added, the processability is reduced and the chemical resistance is not improved.

"0 Effects of the Invention The thermoplastic resin composition of the present invention has styrenic resin ((a)
By adding a liquid crystal polymer (component (b)) to component (component), the chemical resistance, processability, and heat resistance of the styrenic resin are significantly improved. In particular, thermoplastic resins with excellent processability and chemical resistance can be obtained compared to those containing glass fiber filling systems.

In addition, in the thermoplastic resin composition of the present invention, liquid crystal polymer (0) component) and styrene resin ((a) component)
A resin with excellent chemical resistance, processability, and heat resistance can be obtained by improving the compatibility with.

Claims (1)

[Scope of Claims] (a) At least one copolymerizable monomer having at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group is a resin. (b) 10 to 99 weight % of a resin containing aromatic vinyl and/or (meth)acrylic acid alkyl ester as an essential component, copolymerized with 0.1 to 30 weight %; (b) 90 to 1 weight % of a liquid crystal polymer; % of a thermoplastic resin composition.